Met. Mater. Int., Vol. 19, No. 5 (2013), pp.

1131~1137
doi: 10.1007/s12540-013-5032-0

Effect of Surface Area on Corrosion Properties of Magnesium

for Biomaterials
1 1 1, 2, 3
Woo-Cheol Kim , Kwon-Hoon Han , Jung-Gu Kim *, Seok-Jo Yang *, Hyun-Kwang Seok ,
Hyung-Seop Han2,3, and Young-Yul Kim4

1
Sunkyunkwan University, Department of Advanced Materials Engineering,
300 Chunchun-Dong, Jangan-Gu, Suwon 440-746, Korea
2
Chungnam National University, Department of Mechatronics Engineering, Daejeon 305-764, Korea
3
Korean Institute of Science and Technology, Seoul 136-791, Korea
4
Daejeon St. Marys Hospital, Catholic University of Korea, Department of Orthpedics,
Daejeon 301-723, Korea
(received date: 23 October 2012 / accepted date: 24 January 2013)

This study examined the effect of the surface area on the corrosion properties of magnesium through in
vivo (weight loss test) and in vitro (electrochemical and weight loss tests in Hanks solution) tests. The
corrosion rate was reduced as the surface area increased. Surface analysis showed that the precipitation of
calcium phosphate increased with increasing surface area. Moreover, the pH level around the specimen
increased with increasing surface area. This increase of pH can accelerate the precipitation of calcium
phosphate on the surface. However, different mechanism of calcium phosphate precipitation was found for
in vivo and vitro test environment. In vitro environment showed an increase of calcium phosphate due to
the continuous increase in pH, whereas in vivo environment showed increase of calcium phosphate to
maintain homeostasis and reduced the level of pH in physiological system. Consequently, the increase in
magnesium surface area leads to increase the precipitation of calcium phosphate as a more stable rust
layer which ultimately increases the corrosion resistance of magnesium.
Key words: biomaterials, magnesium, implantation, corrosion, scanning electron microscopy(SEM)

1. INTRODUCTION biodegradable polymers have poor mechanical properties

Metallic biomaterials continue to play an important role
in medical applications for the repair or replacement of
bone tissue. Metals are more appropriate for load-bearing
applications compared to polymers or ceramics due to their high
mechanical strength and fracture toughness [1,2]. Conven-
tional metallic implant materials are widely used for orthopedic
bone implant materials. However, the elastic modulus of
these metallic biomaterials is much higher than that of nat-
ural bone and this mismatch causes stress shielding [1,3-7].
Furthermore, metallic biomaterials can release toxic ions
and particles through corrosion or wearing processes to
cause metal allergies, skin diseases and inflammatory cascades
[1,5,8]. Moreover, a second surgical procedure is needed to
remove the metal implant [1,3,9].
Biodegradable polymers, such as polylactic acid (PLA),
polyglicolic acid (PGA) or copolymer (PLDA), have been
used as alternative bone implant materials. However, these
*Corresponding author: kimjg@skku.ac.kr, sjyang@cnu.ac.kr
KIM and Springer, Published 10 September 2013
and an unpredictable degradation rate. Moreover, biodegradable
polymers decrease the pH of body fluids when dissolved in a liv-
ing body, which can damage living tissue [3,5,11]. For these
reasons, the application of biodegradable polymers is limited.
Currently, magnesium and magnesium alloys have attracted
considerable attention as potential biodegradable materials
in medical science due to their similar elastic modulus and
compressive yield strength to natural bone, good biocom-
patibility and positive effects in promoting new bone for-
mation during the biodegradation process [12-14]. These
advantages have prompted considerable amount of researches
to overcome the rapid degradation of magnesium and develop
them into biodegradable orthopedic implants, vascular stents
and bone grafts [1,15-17]. Several methods have been adopted
to improve the biodegradation property, such as element
alloying, Ti-coating and alkaline treatments [17-20]. In addi-
tion, some new magnesium alloys have been developed for
biomedical applications [12,18,21,22].
In general, effect of surface area on corrosion rate is believed
to change according to the anode and cathode ratio. The
corrosion rate of stainless steel and carbon steel, for example,
1132 Woo-Cheol Kim et al.

are reported to increase as their surface area increases [23,24]. Three specimens with different exposed areas were used
When a magnesium-based medical device is being implanted in the immersion test. Before the test, the specimens were
into the human body, the device shape or size must be polished with 600-grit silicon carbide paper, cleaned ultra-
changed according to their purpose or application. These sonically in acetone, and then dried in air. Hanks solution
changes in dimension cause alteration in total magnesium (37 C, pH 7.4, 1 liter) was used as the test solution. The
surface area. Therefore, it is essential to understand the effect specimens were immersed in Hanks solution for 5 days.
of surface area on the corrosion properties of magnesium. The pH of the solution was recorded during the immersion
This study examined the effect of surface area on the corrosion process. After the immersion test, the specimens were removed
mechanism of magnesium using a weight loss and electro- from the solution and cleaned for 20 min in a cleaning
chemical tests in both in vivo and vitro environments. solution (250 g chromium oxide (CrO3) in 1,000 mL water
(H2O)) to remove the surface corrosion products [25]. The
2. EXPERIMENTAL PROCEDURES specimens were then rinsed with distilled water, cleaned
ultrasonically in acetone and dried in open air. The dried
2.1. In vitro test specimens were weighed and the corrosion rate was calcu-
2.1.1. Electrochemical measurement lated using the following equation [26].
Rectangular specimens for the electrochemical test were
87.6W
cut from a commercial pure magnesium ingot and molded CR = --------------- (1)
into epoxy resin with only one side of the area exposed for DAT
the test. Table 1 lists exposed area of the magnesium spec- where CR is the corrosion rate (mm/yr), W is the weight
3 2
imens. The specimen was polished with 600-grit silicon loss (mg), D is the density (g/cm ), A is the area (cm ) and
carbide paper. Hanks solution (pH 7.4, 1 liter) at 37 C was T is the time (hour).
used as the test solution. Table 2 lists the chemical compo-
sition of Hanks solution. 2.2. In vivo test
Electrochemical impedance spectroscopy (EIS) was used The animal studies were performed by the Catholic Uni-
to evaluate the corrosion behavior of the specimens. The speci- versity (Daejeon St. Marys Hospital, Korea) for the evalu-
men was allowed to reach the stable open-circuit potential ation of degradation properties. The experimental protocols
(OCP). The EIS instrumentation consisted of an EG&G were performed in accordance with local regulation (Korea
VMP2 potentiostat and electrochemical impedance soft- animal welfare regulation) and approved by the responsible
ware. The EIS measurements were carried out at OCP with animal care committee (Department of Laboratory Animal,
a 20 mV (rms) perturbation and 6 points per decade. The IACUC, the Catholic University of Korea, CMCDJ-AP-2011-
frequency range was from 100 kHz to 10 mHz. The experimen- 003). Twelve adult SD rats, 600-800 g in weight, were used
tal results were interpreted based on the equivalent circuit in the in vivo experiments (Orient Bio, ChungBuk, Korea).
determined using a suitable fitting procedure described in The implant was placed in the L5-6 disc space posteriorly.
the ZSimpWin program. Animal was anesthetized with 6 mg/dl ketamine and 0.6 mg/dl
2.1.2. Immersion test lumpun with intra-abdominal injections, and the posterior
hair was removed with a shaver and cleaned with alcohol
Table 1. Exposed area of the magnesium specimens and betadine. A vertical incision was made and the muscle
Specimen Exposed area (cm2) fascia was incised with a knife and retracted laterally to
S1 0.25 expose the posterior lamina and small transverse process.
S2 1 Using a curette, the inter-transverse ligament between lam-
S3 2.25 inae was removed and the posterior part of the spine was
exposed to apply each specimen. Muscle fascia and skin
Table 2. Chemical composition of Hanks solution was sutured with nylon and post-surgical care was done to
Component Concentration (g/L) alleviate pain. Animals were sacrificed with CO2 gas and
NaCl 8 posterior spine structures were collected at 5th postopera-
KCl 0.4 tion day for evaluating corrosion rates.
NaHCO3 0.35
NaH2PO4H2O 0.25 2.3. Surface analysis
Na2HPO42H2O 0.06 The corrosion morphology was analyzed by field emis-
MgCl2 0.19 sion scanning electron microscopy (FE-SEM, JEOL JSM-
MgSO47H2O 0.06 6700F). The chemical composition of the surface layer or
Glucose 1 products was determined by energy dispersive x-ray spec-
CaCl22H2O 0.19 troscopy (EDS).
 Effect of Surface Area on Corrosion Properties of Magnesium for Biomaterials
Fig. 1. Nyquist plots for the specimens in Hanks solution as a function of the immersion time: (a) S1, (b) S2, and (c) S3.
3. RESULTS AND DISCUSSION
3.1. In vitro test
3.1.1. Electrochemical measurement
Figure 1 shows the Nyquist plots of the specimens in
Hanks solution during 5 days under the OCP. The imped-
ance spectra of magnesium showed a small semicircle in
the higher frequency region and a large semicircle in the
lower frequency region, indicating the formation of a rust
layer on the magnesium surface. This two-time constant
behavior was caused by a reaction between the substrate
and rust layer and simultaneously between the rust layer
and electrolyte. Figure 2 presents the physical model and
equivalent circuit with fitting EIS data based on the above
impedance spectrum features. The circuit consisted of the
following elements: solution resistance (Rs), two capaci-
tances (C1 and C2), rust layer resistance (Rrust) and charge
transfer resistance (Rct). During the fitting process, the
capacitance was represented by a constant phase element
(CPE) to allow for depressed semicircles.
The corrosion current density of the magnesium was cal-
culated using the following equation assuming that ba and
bc were equal to 0.1 V/decade [27].
Fig. 3. Change in the rust layer and charge transfer resistance in Hanks solution: (a) rust layer resistance, and (b) charge transfer resistance.
1133
Fig. 2. Equivalent circuit for EIS data fitting.
a c
icorr = ------------------------------------------
- (2)
2.3 Rp ( a + c )
The corrosion rate can be estimated from the corrosion cur-
rent density based on Faradays law [28].
0.00327 icorr a
Corrosion rate (mm/y) ----------------------------------------
- (3)
nD
where 0.00327 is the metric and time conversion factor, icorr
2
is the corrosion current density (A/cm ), a is the atomic
weight (g/mol), n is the number of electrons exchanged and
D is the density (g/cm3).
Figure 3 shows the progression of the rust layer and charge
transfer resistance as a function of time in the EIS measure-
1134 Woo-Cheol Kim et al.

Fig. 5. Weight loss test result of magnesium in Hanks solution for 5

Fig. 4. Corrosion rate of the magnesium in Hanks solution as a func- days.
tion of the immersion time.

ments. The resistance values, such as Rrust and Rct are asso-
ciated directly with the corrosion resistance of magnesium.
In particular, the former implies the resistance to the pene-
tration of water and ions through the rust layer, and the latter
denotes the resistance of the reaction rate between the sat-
urated water or ions and the substrate surface. Both Rrust
and Rct in all specimens increased as a function of time due
to the formation of protective film. Concurrently, the resis-
tance of the specimens was in the following order: S3 > S2 >
S1, which suggests that the resistance of the specimens
increased with increasing surface area.
Figure 4 shows the corrosion rate of the specimens as a
function of the immersion time in Hanks solution. The corro-
sion rate of all specimens decreased with immersion time
and increasing surface area. Fig. 6. Change in pH as a function of the immersion time.
As shown in Figs. 3 and 4, the corrosion rate of magne-
sium is associated with the rust layer resistance, which effect [29]. This phenomenon is described by the under-
indicates that the rust layer affects the corrosion properties mining and falling away of second phase particles. Second
of magnesium. Moreover, both the rust layer resistance and phase particles, e.g. iron-rich impurities, are cathodic to the
corrosion rate are affected by the surface area. Therefore, surrounding magnesium matrix, and suffer accelerated local
surface area is a critical factor for determining the corro- corrosion at the particle boundary by microgalvanic corro-
sion properties of magnesium. sion [30-32].
Figure 6 shows the change in pH with immersion time in
3.1.2. Immersion test Hanks solution. The pH of all the specimens increased with
Figure 5 shows the results of the weight loss test of spec- increasing immersion time. In addition, the pH increased with
imens in Hanks solution for 5 days. A similar tendency increasing surface area.
was observed in the EIS test. The corrosion rate decreased The corrosion of magnesium in Hanks solution proceeds
with increasing surface area but the corrosion rate of weight according to the following reactions [33]:
loss test was much higher than that of the EIS test.
2+
For most metal systems, there is usually a good quantita- Mg Mg + 2e (4)
tive agreement between the weight loss and electrochemi-
cal measurements. However, for magnesium, particularly 2H2 O + 2e H2 + 2OH (5)
2+
pure magnesium, the weight loss values are approximately Mg + 2OH Mg ( OH )2 (6)
an order of magnitude higher than that predicted by the
electrochemical test. This is called the negative difference Mg ( OH )2 + 2OH MgCl2 + 2 ( OH ) (7)
 Effect of Surface Area on Corrosion Properties of Magnesium for Biomaterials 1135

According to the above reactions, Mg(OH)2 formed on

the surface of the magnesium specimen. At the same time,
chloride ions can transform Mg(OH)2 into the more soluble
MgCl2. The release of OH- ions in solution by reactions (5)
and (7) increases the solution pH.
For magnesium, corrosion typically takes the form of local-
ized corrosion [34]. However, the localized corrosion of
magnesium has a different mechanism from the autocata-
lytic pitting observed on stainless steels. Localized corrosion
in magnesium is initiated as irregular pits, which spread
laterally and cover the entire surface. There is no tendency
for deep pitting. An attendant increase in pH and stabiliza-
tion of a local Mg(OH)2 film by the production of OH ions
decreases the corrosion rate. The increase of pH leads to
stabilization of Mg(OH)2 film on the surface, which leads
to increase of overall corrosion resistance [35,36]. There-
fore, increased surface area decreased the corrosion rate by
increasing the overall pH level of the solution which cre-
ates stable Mg(OH)2 film on the surface. Fig. 8. Cross-sectional and surface SEM images of magnesium
immersed in Hanks solution for 5 days: (a) S1, (b) S2, and (c) S3.
3.2. In vivo test
Figure 7 shows weight loss measurement of implanted
specimen in rat after the 5-day post operation. It showed a
similar tendency with in vitro and corrosion rate was reduced
as the surface area increased. In the physiological system,
change in the environment is dealt with homeostasis to
maintain equilibrium. When increase in pH proceeds, the
homeostasis plays a buffer role in the physiological system
according to the following reaction [37]:
+
OH + NaH2 PO4 NaHPO4 + H2 O (8)
By the reaction (7), continuous increases of the pH level
in the physiological environment by the implanted magne-
sium specimen can result in necrosis. However, there was
no evidence of necrosis within the implantation site, which

Fig. 7. Weight loss test result of magnesium in vivo environment for Fig. 9. Surface morphology of magnesium implanted in vivo environ-
5 days. ment for 5 days: (a) S1, (b) S2, and (c) S3.
1136 Woo-Cheol Kim et al.

suggests that increased pH is counterbalanced and lowered
to maintain homeostasis. Therefore, in contrast to in vitro
results, in vivo results suggest that there is no drastic change of
pH level within the physiological system.
3.3. Surface analysis
Figure 8 shows SEM cross-sectional and surface mor-
phology of the magnesium specimens immersed in Hanks
solution for 5 days. The results of surface analysis showed
the formation of 1.5 um calcium phosphate layer on top of
the specimen surface. The increase in amount of calcium phos-
phate was observed with the increase in area of specimen
surface. It was due to the increased pH level of the solution
which accelerated the deposition of calcium phosphate [38].
Figure 9 shows SEM cross-sectional images and EDS
analysis of magnesium implanted in rats for 5 days. The
specimens were covered with a rust layer containing Mg,
O, Ca and P and their quantity increased as the surface area
increased. The thickness of the layer was about 3-5 um, which
was relatively thicker than that of in vitro test. Increase of
surface area caused an increase in kinetics of pH level change,
which was similar to the result from in vitro tests. This indicates
that kinetics of the homeostasis (reaction (8)) playing a
buffer role in the physiological system also increases when
the surface area is increased. Ultimately, increase in surface
area causes precipitation of calcium phosphate within the

Fig. 10. Schematic diagram of the mechanism for improving the rust layer resistance by calcium phosphate: (a) in vitro, and (b) in vivo.
 Effect of Surface Area on Corrosion Properties of Magnesium for Biomaterials
rust layer to form a more stable rust layer.
Figure 10 shows increased corrosion resistance mecha-
nism due to the increase of pH in both in vivo and in vitro
systems. In vitro process (Fig. 10(a)) can be divided into
three steps. Firstly, solutions pH level increases with the
increase in surface area. Secondly, accelerated deposition
of calcium phosphate by the increased pH leads to stabili-
zation of Mg(OH)2 film. Finally, stable protective layer is
formed, which increases the corrosion resistance of the
magnesium. Therefore, a high pH environment maintains a
more stable protective layer continuously than a low pH one.
For in vivo system (Fig. 10(b)), increase in surface area
causes an increase in pH level and leads to increased con-
centration of phosphate from homeostasis. It is evident that
increased surface area results in formation of more stable rust
layer which ultimately increases the corrosion resistance of
magnesium.
4. CONCLUSIONS
This study examined the effect of surface area on the cor-
rosion mechanism of magnesium through in vitro and vivo
tests. In vitro test showed an increase of calcium phosphate
due to the continuous increase in pH, which leads to the
formation of stable rust layer decreasing the corrosion rate.
In vivo test showed an increase in surface area causes an
increase in pH level and led to increased concentration of
phosphate from homeostasis. Increased quantity of the phos-
phate within the physiological system along with the calcium
resulted in the formation of more stable rust layer which
ultimately decreases the corrosion rate of magnesium. Con-
sequentially, increase in magnesium surface area leads to
increase in precipitation of calcium phosphate and causes a
reduction in corrosion rate.
ACKNOWLEDGMENTS
This study was supported by a grant of the Korea Health-
care Technology R&D Project, Ministry of Health & Wel-
fare, Republic of Korea (A101942).
REFERENCES
1. M. P. Staiger, A. M. Pietak, J. Huadmai, and G. Dias, Biom-
aterials 27, 1728 (2006).
2. M. Niinomi, Metall. Mater. Trans A 33, 477 (2002).
3. J. Y. Lee, G. S. Han, Y. C. Kim, J. Y. Byun, J. I. Jang, H. K.
Seok, and S. J. Yang, Met. Mater. Int. 1, 955 (2009).
4. F. Witte, N. Hort, C. Vogt, S. Cohen, K. U. Kainer, R. Wil-
lumeit, and F. Feyerabend, Curr. Opi. Solid State. Mat. Sci.
12, 63 (2008).
5. E. Zhang, L. Xu, G. Yu, F. Pan, and K. Yang, J. Biomed.
Mater. Res. Part A 90, 882 (2009).
1137
6. D. R. Sumner and J. O. Galante, Clin. Orhop. Relat. Res.
274, 202 (1992).
7. J. Nagels, M. Stokdijk, and P. M. Rozing, Shoulder Elb.
Surg. 12, 35 (2003).
8. D. A. Puleo and W. W. Huh, J. Appl. Biomater. 6, 109 (1995).
9. G. Mani, M. D. Feldman, D. Patel, and C. M. Agrawal, Bioma-
terials 28, 1689 (2007).
10. G. O. Hofmann, Arch. Orthop. Traum. Su. 114, 123 (1995).
11. O. Bostman and H. Pihlajamaki, Biomaterials 21, 2615 (2000).
12. Z. Li, X. Gu, S. Lou, and Y. Zheng, Biomaterials 29, 1329 (2008).
13. L. Xu, F. Pan, G. Yu, L. Yang, E. Zhang, and K. Yang, Bio-
materials 30, 1512 (2009).
14. W. D. Mueller, M. L. Nascimento, and M. F. Lorenzo, Acta
Biomater. 6, 1749 (2010).
15. F. Witte, V. Kaese, H. Haferkamp, E. Switzer, A. Meyer-
Lindenberg, and C. J. Wirth, Biomaterials 26, 3557 (2005).
16. J. E. Gray-Munro and M. Strong, J. Biomed. Mater. Res A
90, 339 (2008).
17. M. B. Kannan and R. K. S. Raman, Biomaterials 29, 2306
(2008).
18. E. Zhang, W. He, H. Du, and K. Yang, Mater. Sci. Eng. A
488, 102 (2008).
19. E. Zhang, L. Xu, and K. Yang, Scripta Mater. 53, 523 (2005).
20. L. Li, J. Gao, and Y. Wang, Surf. Coat. Technol. 185, 92 (2004).
21. L. Xu, G. Yu, E. Zhang, F. Pan, and K. Yang, J. Biomed.
Mater. Res. A 83, 703 (2007).
22. E. Zhang and L. Yang, Mater. Sci. Eng. A 97, 111 (2008).
23. M. J. Kim, Y. W. Jang, Y. H. Yoo, J. J. Kim, and J. G. Kim,
J. Kor. Electro. Soc. 13, 96 (2010).
24. G. T. Burstein and G. O. Ilevbare, Corros. Sci. 38, 2257 (1996).
25. J. G. Kim and S. J. Koo, Corrosion 56, 380 (2000).
26. D. A. Jones, Principles and Prevention of Corrosion, 2nd
ed., p.31, Prentice-Hall, NJ (1996).
27. D. A. Jones, Principles and Prevention of Corrosion, 2nd
ed., p.148, Prentice-Hall, NJ (1996).
28. D. A. Jones, Principles and Prevention of Corrosion, 2nd
ed., p.76, Prentice-Hall, NJ (1996).
29. M. M. Avedesian, H. Baker, Magnesium and Magnesium
Alloys, p.200, ASM Internatinal, USA (1999).
30. G. Song, A. Atrens, D. Stjohn, J. Nairn, and Y. Li, Corros.
Sci. 39, 855 (1997).
31. C. D. Yim, Y. M. Kim, S. H. Park, and B. S. You, Korean J.
Met. Mater. 50, 619 (2012).
32. G. Song, A. Atrens and M. Dargusch, Corros. Sci. 41, 249 (1999).
33. S. Zhang, X. Zhang, C. Zhao, J. Li, Y. Song, C. Xie, H.
Tao, Y. Zhang, Y. He, Y. Jiang, and Y. Bian, Acta Biomater.
6, 626 (2010).
34. G. Song and A. Atrens, Adv. Eng. Mater. 9, 177 (2007).
35. G. Song and A. Atrens, Adv. Eng. Mater. 1, 11 (1999).
36. M. M. Avedesian and H. Baker, Magnesium and Magne-
sium Alloys, p.194, ASM Internatinal, USA (1999).
37. C. Guyton, Hall, Textbook of Medical Physiology, p.391,
Elsevier Science, Singapore (2002).
38. L. Yang and E. Zhang, Mater. Sci. Eng. C 29, 1691 (2009).